Hydroxylation of the Zn terminated ZnO(0 0 0 1) surface under vacuum conditions

Abstract

Under vacuum conditions, the polar surface ZnO(0 0 0 1) evolves in time forming a layer with H and additional O which changes the top layer stoichiometry and other properties such as its work function. In this work we present a study of the evolution of the ZnO(0 0 0 1) surface in ultra-high vacuum performed with time of flight direct recoil spectroscopy to detect the adsorbed H and O, plus other standard techniques including photoelectron spectroscopy and low energy electron diffraction. The experimental results are complemented with density functional theory (DFT) calculations for surfaces perfectly terminated and with triangular defects plus O adatoms. We show that the ZnO surface reaches a stable condition at an OH coverage of around 0.25 ML. We also studied the effect of increasing the partial pressure of H2 and of H2O on the layer growth. We observe that during the formation of the OH layer the work function decreases. Analysis of this variation of the work function with DFT reveals the role of the O adatoms in the adsorption process. Finally we show that the OH coverage decreases continuously with the increase of the sample temperature, without showing a well-defined desorption peak, which is in agreement with earlier predictions of the thermodynamics evolution. We believe that the present results contribute to clarify the behavior of the ZnO(0 0 0 1) surface under vacuum and will be useful in future works, particularly where H cannot be detected by standard techniques.